The present invention relates to oligomeric and/or polymeric, radiation-reactive precursor stages of polyimides, polyisoindoloquinazoline diones, polyoxazine diones and polyquinazoline diones as well as to a method for manufacturing these radiation-reactive precursor stages.
Precursor stages of the type mentioned, which are soluble in organic solvents, are known, for example, from German Pat. No. 2 308 830 or the corresponding U.S. Pat. No. 3,957,512. The known polymer precursor stages are polyaddition or polycondensation products of polyfunctional carbocyclic or heterocyclic compounds, carrying radiation-sensitive radicals, with diamines, diisocyanates, bis-acid chlorides and dicarboxylic acids. The compounds carrying radiation-sensitive radicals contain two carboxyl, carboxylic acid chloride, amino, isocyanate or hydroxyl groups suitable for addition or condensation reactions and, partially, in ortho- or peri-position thereto, radiation-reactive groups bound to carboxyl groups in ester-fashion, and the diamines, diisocyanates, bis-acid chlorides and dicarboxylic acids to be reacted with these compounds have at least one cyclic structure element.
Radiation-reactive polyimide precursor stages are prepared in particular in such a manner that unsaturated alcohols such as allyl alcohol are added on tetracarboxylic acid dianhydrides such as pyromellitic-acid dianhydride, the liberated carboxylic-acid groups of the diesters then formed are converted into acid chloride groups, and the diester-bis-acid-chlorides are subjected to a polycondensation reaction with a diamine (usually aromatic) such as diaminodiphenyl ether. If diamino compounds are used which have amido groups in ortho-position, polyisoindoloquinazoline diones are produced in a similar manner.
Polyoxazine dione precursor stages are produced by polyaddition of diisocyanates such as diphenylmethane diisocyanate, on phenolic hydroxyl groups of olefinically unsaturated diesters such as methylene disalicyclic-acid ester and, in a similar manner, polyquinazoline diones are prepared by polyaddition of diisocyanates on amino groups of olefinically unsaturated diesters.
The known preparation methods generally require several reaction stages and low temperatures. In addition, if acid chlorides are used, intensive purification of the reaction products is required and the synthesis of unsaturated diesters of the kind mentioned is difficult to carry out.